Cyclic halogen containing rubber derivatives



Patented Mar. 7, 1939 UNITED STATES 2,149,484 PATENT GFFECE CYCLIC HALOGEN CONTAINING RUBBER DERIVATIVES Herbert A. Winkelmann and Eugene W. Moffett. Chicago, Ill., assignors to Marbon Corporation, a corporation of Delaware N Drawing. Application October 31, 1936,

Serial No. 108,682

2 Claims. (Cl. 260-411) This invention relates to a rubber derivative and to a method for making same. More particularly itrelates to a low chlorine containing, hard, brittle, resinous reaction product of rubber 5:.- and hydrogen chloride.

It is known that hydrogen chloride will add to the double bonds of a rubber molecule, that the e, and be a non-tacky, moderately hard, tough plastic. As the chlorine content goes below 25% the tackiness of the product becomes pronounced, and the resemblance in to unvulcanized rubber increases.

1 I known that by treating rubber with chlorostannic products. Our products contain more chlorine than the chlorostannic acid-rubber reaction products, and less chlorine than the saturated rubber hydrochlorides. Our products are less unsatuo rated than rubber hydrochloride of the same chlorine content, and are also free from amphoteric metal halides.

The process of our invention essentially comprises reacting solid rubber with hydrogen chloride at high temperatures and great speed. Our preferred method is to contact powdered rubber with gaseous hydrogen chloride under superatmospheric pressure. The resulting reaction is exothermic and extremely fast. 50 No attempt is made to cool the mass or otherwise regulate the temperature. The resulting temperature is so high that fusion takes place. The resulting product is hard and brittle, breaking with a conchoidal fracture. It is relatively insoluble in benzol and chlorinated solvents.

understood. If powdered rubber and liquefied 60 hydrogen chloride are reacted under controlled ous product obtained Heating of rubber hydrochloride likewise does not give our brittle, resinous product.

produces such conditions.

The following example will illustrate our invention: Powdered rubber sufiiciently fine to pass 'a 30 mesh screen and consisting of substantially 300 lbs. per A temperature of 130 C. was observed but the actual temperature within the mass was probably much higher since the mass had fused and flowed together. Two runs were made, D1 and D2. The iodine number on D1 was 100.9; on Dz104.3. The chlorine content of D1 was 5.6%, of Dz4%. Assuming the originally powdered rubber was pure it is possible to calcu- Percent used by HO] ercent showed by iodine No Percent unsaturation lost The reaction products D1 and D2 were also treated with liquefied hydrogen chloride, 2. reagent which reacts extremely fast with rubber. The chlorine analysis before and after treatment was as follows:

Before After Gain Percent Percent Percent D 6 7. 2. 2 D2 4. 0 8.0 4. 0

The reaction products D1 and D2 were compared with other halogen containing rubber derivatives.

The following table gives comparative chlorine contents and specific gravities'.

7 Table I Percent v I chlorine Ohlorostannic acid rubber derivative (Pliohte) 1.6 0.981.00 Rubber hydrochloride obtained by reacting solid sheet rubber with hydrogen chloride 7 at 100 C 31. 6 1.157 D; 5. 6 1.000 D: l 4. .j

The following table gives the percent residue from a .5 gram of sample in 50 cc. of gasoline or benzol run at room temperature and at 60 C. I

Table II 20 Benzol I Gasoline 25 (Philolite) o o 0 High temperature rubber hydrochlo- V ride. 100 97.4 100 100 The products of our invention are chlorine containing rubber derivatives of less unsaturation than rubber hydrochlorides of the same chlorine content, and of higher resistance to solvents than the reaction products of rubber and chlorostannic acid or'rubber and stannic chloride. They are of resinous, brittle character and may "be milled and molded into various articles of manufacture in a manner similar to other thermoplastic resins and plastics.

"It'is to be understood that various details may be varied without departing from the spirit of this invention; The rubber is preferably powdered or otherwise divided soas to give a large area of exposed surface. The powdered rubber mayicontain amphoteric metal compounds intimately admixed, but this is not essential. However, powdered'rubber containing zinc stearate powder admixed has been found very satisfactory. We claim:- I

'.1..The method of densation derivative of rubber which comprises subjecting a mass of finely divided particles of rubber to hydrogen chloride :under'pressure' of the'order of 300 pounds per square inch'to bring about an exothermic reaction, and allowing the reaction to proceed at such a speed and'tem-v perature as to fuse the mass of reacted particles.

2. The method of making a resin-like con densation derivative of rubber which comprises subjecting a mass of powdered rubber to gaseous hydrogen chloride under superatmospheric pressure to bring about an exothermic reaction, :and. allowing the reaction to proceed at such speed' and temperature as to fuse the mass. HERBERT A. WINKELMANN. EUGENE W. MOFFETT.

making a resin-like"con-- 

